Solvent-mediated outer-sphere CO2 electro-reduction mechanism over the Ag111 surface
The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism und...
Uložené v:
| Vydané v: | Chemical science (Cambridge) Ročník 13; číslo 13; s. 3803 - 3808 |
|---|---|
| Hlavní autori: | , , |
| Médium: | Journal Article |
| Jazyk: | English |
| Vydavateľské údaje: |
Cambridge
Royal Society of Chemistry
30.03.2022
The Royal Society of Chemistry |
| Predmet: | |
| ISSN: | 2041-6520, 2041-6539 |
| On-line prístup: | Získať plný text |
| Tagy: |
Pridať tag
Žiadne tagy, Buďte prvý, kto otaguje tento záznam!
|
| Abstract | The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL. |
|---|---|
| AbstractList | The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL. In addition to the commonly accepted inner-sphere mechanism for e− transfer, we show that an outer-sphere electron transfer from the cathode to CO2 is operable at high overpotentials. The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2 via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL.The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2 via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL. The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR process is instrumental for the better design of electrodes operable at low overpotentials with high current density. The catalytic mechanism underlying the turnover and selectivity of the CO2RR is modulated by the nature of the electrocatalyst, as well as the electrolyte liquid, and its ionic components that form the electrical double layer (EDL). Herein we demonstrate the critical non-innocent role of the EDL for the activation and conversion of CO2 at a high cathodic bias for electrocatalytic conversion over a silver surface as a representative low-cost model cathode. By using a multiscale modeling approach we demonstrate that under such conditions a dense EDL is formed, which hinders the diffusion of CO2 towards the Ag111 electrocatalyst surface. By combining DFT calculations and ab initio molecular dynamics simulations we identify favorable pathways for CO2 reduction directly over the EDL without the need for adsorption to the catalyst surface. The dense EDL promotes homogeneous phase reduction of CO2via electron transfer from the surface to the electrolyte. Such an outer-sphere mechanism favors the formation of formate as the CO2RR product. The formate can undergo dehydration to CO via a transition state stabilized by solvated alkali cations in the EDL. |
| Author | Khramenkova, Elena Sinha, Vivek Pidko, Evgeny A |
| Author_xml | – sequence: 1 givenname: Vivek surname: Sinha fullname: Sinha, Vivek – sequence: 2 givenname: Elena surname: Khramenkova fullname: Khramenkova, Elena – sequence: 3 givenname: Evgeny surname: Pidko middlename: A fullname: Pidko, Evgeny A |
| BookMark | eNpdkM1Lw0AQxRep2Fp78S8IePES3d3Zj-QilOIXFHqwnsNmM2lSkmzdTQr-96Yogs5lBt7jMb93SSad65CQa0bvGIX0vmDBUs1Yuj8jM04Fi5WEdPJ7czolixD2dBwAJrm-IFOQAnhK5Yxs31xzxK6PWyxq02MRuaFHH4dDhR6j1YZH2KDtvYs9FoPta9dFLdrKdHVoI3dEH_UVRssdYywKgy-NxStyXpom4OJnz8n70-N29RKvN8-vq-U63oOGPkYKlFlW0LRUJSYJl6xI8wSkVonUJQgsAYUymmuppJVQ5tzkVkFhQJtcwJw8fOcehnz8344c3jTZwdet8Z-ZM3X2V-nqKtu5Y5akSik4Bdz-BHj3MWDos7YOFpvGdOiGkPFTf2NrIEfrzT_r3g2-G_FGlxCJSPgI9QVorHpJ |
| ContentType | Journal Article |
| Copyright | Copyright Royal Society of Chemistry 2022 This journal is © The Royal Society of Chemistry. This journal is © The Royal Society of Chemistry 2022 The Royal Society of Chemistry |
| Copyright_xml | – notice: Copyright Royal Society of Chemistry 2022 – notice: This journal is © The Royal Society of Chemistry. – notice: This journal is © The Royal Society of Chemistry 2022 The Royal Society of Chemistry |
| DBID | 7SR 8BQ 8FD JG9 7X8 5PM |
| DOI | 10.1039/d1sc07119j |
| DatabaseName | Engineered Materials Abstracts METADEX Technology Research Database Materials Research Database MEDLINE - Academic PubMed Central (Full Participant titles) |
| DatabaseTitle | Materials Research Database Engineered Materials Abstracts Technology Research Database METADEX MEDLINE - Academic |
| DatabaseTitleList | MEDLINE - Academic Materials Research Database |
| Database_xml | – sequence: 1 dbid: 7X8 name: MEDLINE - Academic url: https://search.proquest.com/medline sourceTypes: Aggregation Database |
| DeliveryMethod | fulltext_linktorsrc |
| Discipline | Chemistry |
| EISSN | 2041-6539 |
| EndPage | 3808 |
| ExternalDocumentID | PMC8966634 |
| GrantInformation_xml | – fundername: ; grantid: ARC.CBBC 2016.008 – fundername: ; grantid: 725686 |
| GroupedDBID | 0-7 0R~ 53G 705 7SR 7~J 8BQ 8FD AAFWJ AAIWI AAJAE AARTK AAXHV ABEMK ABIQK ABPDG ABXOH ACGFS ACIWK ADBBV ADMRA AEFDR AENEX AESAV AFLYV AFPKN AGEGJ AGRSR AHGCF AKBGW ALMA_UNASSIGNED_HOLDINGS ANUXI AOIJS APEMP AUDPV AZFZN BCNDV BLAPV BSQNT C6K D0L EE0 EF- F5P GROUPED_DOAJ H13 HYE HZ~ H~N JG9 O-G O9- OK1 PGMZT R7C R7D RAOCF RCNCU RNS RPM RRC RSCEA RVUXY SKA SKF SKH SKJ SKM SKR SKZ SLC SLF SLH 7X8 5PM AGMRB |
| ID | FETCH-LOGICAL-j373t-e0301c1d09f6fe88251d9b83576857f34ef3e46a727565c53fb2abc63da37ab43 |
| ISICitedReferencesCount | 20 |
| ISICitedReferencesURI | http://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=Summon&SrcAuth=ProQuest&DestLinkType=CitingArticles&DestApp=WOS_CPL&KeyUT=000766790700001&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| ISSN | 2041-6520 |
| IngestDate | Tue Nov 04 01:49:18 EST 2025 Thu Sep 04 20:10:40 EDT 2025 Fri Jul 25 03:23:10 EDT 2025 |
| IsDoiOpenAccess | true |
| IsOpenAccess | true |
| IsPeerReviewed | true |
| IsScholarly | true |
| Issue | 13 |
| Language | English |
| LinkModel | OpenURL |
| MergedId | FETCHMERGED-LOGICAL-j373t-e0301c1d09f6fe88251d9b83576857f34ef3e46a727565c53fb2abc63da37ab43 |
| Notes | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23 |
| ORCID | 0000-0001-9242-9901 0000-0002-6856-9469 |
| OpenAccessLink | http://dx.doi.org/10.1039/d1sc07119j |
| PMID | 35432905 |
| PQID | 2644848237 |
| PQPubID | 2047492 |
| PageCount | 6 |
| ParticipantIDs | pubmedcentral_primary_oai_pubmedcentral_nih_gov_8966634 proquest_miscellaneous_2652033135 proquest_journals_2644848237 |
| PublicationCentury | 2000 |
| PublicationDate | 2022-03-30 |
| PublicationDateYYYYMMDD | 2022-03-30 |
| PublicationDate_xml | – month: 03 year: 2022 text: 2022-03-30 day: 30 |
| PublicationDecade | 2020 |
| PublicationPlace | Cambridge |
| PublicationPlace_xml | – name: Cambridge |
| PublicationTitle | Chemical science (Cambridge) |
| PublicationYear | 2022 |
| Publisher | Royal Society of Chemistry The Royal Society of Chemistry |
| Publisher_xml | – name: Royal Society of Chemistry – name: The Royal Society of Chemistry |
| SSID | ssj0000331527 |
| Score | 2.4639294 |
| Snippet | The electrocatalytic CO2 reduction reaction (CO2RR) is one of the key technologies of the clean energy economy. Molecular-level understanding of the CO2RR... |
| SourceID | pubmedcentral proquest |
| SourceType | Open Access Repository Aggregation Database |
| StartPage | 3803 |
| SubjectTerms | Carbon dioxide Chemical reduction Chemistry Clean energy Conversion Dehydration Electrocatalysts Electrolytes Electron transfer Molecular dynamics Selectivity |
| Title | Solvent-mediated outer-sphere CO2 electro-reduction mechanism over the Ag111 surface |
| URI | https://www.proquest.com/docview/2644848237 https://www.proquest.com/docview/2652033135 https://pubmed.ncbi.nlm.nih.gov/PMC8966634 |
| Volume | 13 |
| WOSCitedRecordID | wos000766790700001&url=https%3A%2F%2Fcvtisr.summon.serialssolutions.com%2F%23%21%2Fsearch%3Fho%3Df%26include.ft.matches%3Dt%26l%3Dnull%26q%3D |
| hasFullText | 1 |
| inHoldings | 1 |
| isFullTextHit | |
| isPrint | |
| journalDatabaseRights | – providerCode: PRVAON databaseName: DOAJ Directory of Open Access Journals customDbUrl: eissn: 2041-6539 dateEnd: 99991231 omitProxy: false ssIdentifier: ssj0000331527 issn: 2041-6520 databaseCode: DOA dateStart: 20150101 isFulltext: true titleUrlDefault: https://www.doaj.org/ providerName: Directory of Open Access Journals – providerCode: PRVAUL databaseName: Royal Society of Chemistry customDbUrl: eissn: 2041-6539 dateEnd: 99991231 omitProxy: false ssIdentifier: ssj0000331527 issn: 2041-6520 databaseCode: RRC dateStart: 20100101 isFulltext: true titleUrlDefault: https://pubs.rsc.org/ providerName: Royal Society of Chemistry |
| link | http://cvtisr.summon.serialssolutions.com/2.0.0/link/0/eLvHCXMwtV1bb9MwFLbYQIIXxFUUxmQkxEsVkcRxLo-o6oRE1U1ahvoWOY7Nug2nNG01_j3nOJcm7GU88BJVSZWm_pxjn8v3HUI-JhpnClY1chu64doRObyPKB7FPRkzWVh1_Vk0n8eLRXLWMK4r204gMia-vU1W_xVqOAdgI3X2H-Dubgon4DOADkeAHY73Av68vMEaRsdyQnA_WWLXBqdC_QA1npz646b1jbNG2VaL_0-FBGDsl4EVnTXd5AfYp3G1XWshh3oGrcRAywjCPHDL_OoFFs6Xpk4mfQeD2vGBvl1iNZi5LneiripTplsYzpbFtY3cTnfw7343YdYmJAHeLHL03L3l8t3Ac0LuuwMzy_rTifWMJoutzMFda-4yFEMtvErCRshLrvZrVpunn59mJxezWZZOF-mn1S8Hu4lh1r1prXJAHvoRT7yeq21XaMaabr7dk7bKtSz5vP-9gdcxrJntbULSZ-Rp4z3QLzXqz8kDZV6Qx5O2ad9Lkv6NPu2jTwF9egd92qFPEX0K6FOLPm3Qf0UuTqbp5KvTNM5wrljENo5CP1d6hZvoUKsY2clFksNeG3xLHmkWKM1UEIoItf-55EznvshlyArBIpEH7DU5NKVRbwjViRB5kevCz8GXDmPhJTLKpSwCnXMugxE5aocoa16CKrNOf4AySCPyobsMI4HJKGFUucXvwKgDDoyPSDQY2mxV66xkqHw-vGKWl1YBPQYnPWTB23vc_R15sp-iR-Rws96q9-SR3G2W1fqYHESL-NjOjj-3mXzb |
| linkProvider | Directory of Open Access Journals |
| openUrl | ctx_ver=Z39.88-2004&ctx_enc=info%3Aofi%2Fenc%3AUTF-8&rfr_id=info%3Asid%2Fsummon.serialssolutions.com&rft_val_fmt=info%3Aofi%2Ffmt%3Akev%3Amtx%3Ajournal&rft.genre=article&rft.atitle=Solvent-mediated+outer-sphere+CO2+electro-reduction+mechanism+over+the+Ag111+surface&rft.jtitle=Chemical+science+%28Cambridge%29&rft.au=Sinha%2C+Vivek&rft.au=Khramenkova%2C+Elena&rft.au=Pidko%2C+Evgeny+A&rft.date=2022-03-30&rft.issn=2041-6520&rft.volume=13&rft.issue=13&rft.spage=3803&rft_id=info:doi/10.1039%2Fd1sc07119j&rft.externalDBID=NO_FULL_TEXT |
| thumbnail_l | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/lc.gif&issn=2041-6520&client=summon |
| thumbnail_m | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/mc.gif&issn=2041-6520&client=summon |
| thumbnail_s | http://covers-cdn.summon.serialssolutions.com/index.aspx?isbn=/sc.gif&issn=2041-6520&client=summon |